Detergent Or Cleaning Agent Comprising At Least Two Phases

ABSTRACT

A detergent or cleaning agent, in particular a cleaning agent for hard surfaces, having at least two phases which are different from each other. The detergent or cleaning agent includes at least one first phase and at least one second phase that is different, with the at least one first phase being solid and the at least one second phase having at least one polymer and at least one polyvalent alcohol.

FIELD OF THE INVENTION

The present invention relates to a detergent or cleaning agent,particularly a cleaning agent for hard surfaces, with at least twomutually different phases.

BACKGROUND OF THE INVENTION

Detergents or cleaning agents are usually present in solid form (as apowder, for example) or in liquid form (or also as a flowing gel).Liquid detergents or cleaning agents in particular are increasinglypopular with consumers.

Solid detergents or cleaning agents have the advantage that, unlikeliquid detergents or cleaning agents, do not require any preservatives.Liquid product formats are increasingly gaining acceptance in themarket, particularly due to their quick solubility and the resultingquick availability of the active ingredients they contain. This givesthe consumer the option of using abbreviated rinse cycles while stillobtaining good cleaning performance.

Furthermore, consumers have grown accustomed to the convenient meteringof preportioned machine detergents or cleaning agents, such asdishwashing detergents, and use these products in the form of tablets(solid detergents or cleaning agents) or in the form of pouches that arefilled with what is usually a liquid detergent or cleaning agent,although powder-filled pouches are possible as single-use portions.Single-use portions in water-soluble pouches are popular with consumersnot only because they no longer come into contact with the chemicalcomposition, but rather not least because of the attractive appearanceof the pouches. The appearance of the dosage form is becomingincreasingly important. Besides good cleaning performance and sufficientstorage stability, a good appearance is one of the reasons on which theselection of a product is based. However, products that are stored inpouches frequently change their visual appearance, which consumers oftenassociate with reduced capacity and degraded cleaning performance.

From the perspective of consumers, it would be desirable to combine theadvantages of both product formats and make available a dosage form thatis improved compared to the prior art, particularly for detergents orcleaning agents that are usually liquids. Both single-use portioning anda visual appearance that is attractive to consumers should be achievedsimultaneously. Surprisingly, it was found that this object can beachieved through the formulation of a flexible phase that is combinedwith a solid phase.

BRIEF SUMMARY OF THE INVENTION

In a first embodiment, the object on which the present application isbased is thus achieved by a detergent or cleaning agent that comprisesat least one first phase and at least one second phase that is differenttherefrom, with the at least one first phase being solid and the atleast one second phase comprising at least one polymer and at least onepolyvalent alcohol.

In terms of the present invention, a phase is a spatial region in whichphysical parameters and the chemical composition are homogeneous. Onephase differs from another phase through its different features, such asingredients, physical properties, external appearance, etc. Preferably,different phases can be differentiated visually from one another. Afirst phase can thus be clearly distinguished by a consumer from the atleast one second phase. If the detergent or cleaning agent according tothe invention has more than one first phase, then they can also each bedistinguished from one another with the naked eye because of theirdifferent coloration, for example. The same holds when two or moresecond phases are present. In this case as well, a visualdifferentiation of the phases, for example on the basis of a differentin coloration or transparency, is possible. In terms of the presentinvention, phases are thus self-contained regions that can bedifferentiated visually from one another by a consumer with the nakedeye. The individual phases can have different characteristics when used,such as the speed with which the phase dissolves in water and hence thespeed and the sequence of the release of the ingredients contained inthe respective phase.

According to the invention, the at least one second phase isdimensionally stable at room temperature. During manufacture, the atleast one polymer is brought into contact with the at least onepolyvalent alcohol. This enables a flowable mixture to be obtained thatcan be molded as desired. After a certain period of time, a second phaseis obtained that remains in the predefined shape, i.e., is dimensionallystable. This time period, the setting time, is preferably 15 minutes orless, more preferably 10 minutes or less, especially preferably 5minutes. The at least one second phase yields on pressure but is notdeformed as a result, but rather returns to its initial state after thepressure has been removed. The at least one second phase is preferablyelastic, particularly linear-elastic. The at least one second phase isalso preferably transparent, whereby a good visual impression isachieved.

The at least one second phase is sliceable. For example, it can be cutwith a knife after it sets without being destroyed beyond the cut thatis made. Moreover, the at least one second is particularly flexible. Dueto its flexibility and elasticity, it can assume any shape. This alsomeans that it has a level of breaking strength that enables goodhandling, particularly in terms of transport and storage, but alsoconsumption.

These and other aspects, features, and advantages of the invention willbecome apparent to a person skilled in the art through the study of thefollowing detailed description. Any feature from one aspect of theinvention can be used in any other aspect of the invention. Furthermore,it will readily be understood that the examples contained herein areintended to describe and illustrate but not to limit the invention andthat, in particular, the invention is not limited to these examples.Unless indicated otherwise, all percentages indicated are percent byweight. Numerical ranges that are given in the format “from x to y”include the cited values. If several preferred numerical ranges areindicated in this format, it is self-evident that all ranges that resultfrom the combination of the various endpoints are also included.

As used herein, “at least one” refers to 1 or more, i.e., 1, 2, 3, 4, 5,6, 7, 8, 9, or more. In relation to an ingredient, the expression refersto the type of ingredient and not to the absolute number of molecules.“At least one bleach catalyst” therefore means at least one type ofbleach catalyst, for example—that is, that one type of bleach catalystor a mixture of several different bleach catalysts can be used. Togetherwith weight data, the expression refers to all compounds of theindicated type that are contained in the composition/mixture, that is,that the composition does not contain any other compounds of this typebeyond the indicated quantity of the corresponding compounds.

When reference is made herein to molar masses, this information alwaysrefers to the number-average molar mass M_(n) unless explicitlyindicated otherwise. The number average of the molar mass can bedetermined, for example, by means of gel permeation chromatography (GPC)according to DIN 55672-1:2007-08 with THF as the eluent. Thenumber-average molar mass M_(w) can also be determined by means of GPCas described for M_(n).

Unless explicitly indicated otherwise, all percentages that are cited inconnection with the compositions described herein refer to wt % (percentby weight) with respect to the respective mixture.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically shows the arrangement of a first phase (1) on ornext to a second phase (2);

FIG. 2a shows a first phase (1) surrounded by a second phase (2);

FIG. 2b shows a second phase (2) surrounded by a first phase (1);

FIG. 3a schematically shows the embedding of a first phase (1) in asecond phase (2);

FIG. 3b schematically shows the embedding of a second phase (2) in afirst phase (1); and

FIG. 4 schematically shows the arrangement of the second phase (2), inthe form of a core, embedded in the first phase (1).

DETAILED DESCRIPTION OF THE INVENTION

In a preferred embodiment, the at least one first phase is present incompressed form. In this embodiment, the detergent or cleaning agentaccording to the invention thus comprises at least one first solid,compressed phase as well as at least one second phase that comprises atleast one polymer as well as at least one polyvalent alcohol.

Certain minimum requirements are placed on formulations of the at leastone second phase. For instance, as already stated, the second phase mustalways set within as short a time as possible. Long setting times wouldresult in excessively long production times and thus to high costs.According to the invention, “setting time” refers to the period of timeduring production within which the at least one second phase goes from aflowable state to a state that is non-flowable and dimensionally stableat room temperature. Room temperature is to be understood as atemperature of 20° C. Without constituting a restriction, this can bedone through the crosslinking of the at least one polymer.

Furthermore, the second phase must be stable in storage, particularly incommon storage conditions. The second phase according to the inventionis a component of a detergent or cleaning agent. Detergents or cleaningagents are usually stored for a certain period of time in a household.They are usually stored near the washing machine. The second phaseshould be stable in such storage conditions. Therefore, the second phaseshould be stable and not deform or otherwise change in consistency overa storage period of 4 to 12, particularly 10 to 12 weeks or longer at atemperature of up to 40° C., especially 30° C., particularly 25° C. or20° C.

The surface of the second phase should differ clearly from the firstphase by a distinct luster, for example. The surface of the solid atleast one first phase is usually not glossy but rather matte, dull, ormuted, so that it is possible to make a clear distinction through theluster that makes the detergent or cleaning agent attractive toconsumers.

A change in volume or shrinkage during storage would be disadvantageous,since that would diminish consumers' acceptance of the product. Theemergence of liquid or the sweating-out of components from the secondphase is also not desired. Here, too, the visual impression is relevant,for one. The stability of the second phase can be influenced by theleakage of liquid, such as solvent, for example, so that the componentsare no longer stably contained, which can also impact the detergent orcleaning effect.

Moreover, it should be possible for the at least one first phase and theat least one second phase to be in direct contact with one another. Inthis case, there should no negative interaction between the first phaseand the second phase. What no negative interaction means here, forexample, is that no ingredients or solvents go from one phase into theother or that the stability, particularly storage stability, preferablyfor 4 weeks and a storage temperature of 30° C., and/or the aestheticsof the product are not impaired in any way, for example through a changein color, the formation of wet-looking edges, a blurred boundary betweenthe two phases, or the like.

Surprisingly, it was found that an especially high level of storagestability is achieved if the second phase is substantially water-free.This means that the second phase is preferably substantially free ofwater. “Substantially free” means here that small quantities of watercan be contained in the second phase. For example, this water can beintroduced into the phase through a solvent or as crystallization wateror as a result of reactions of components of the phase with each other.However, no water is introduced as a solvent for the manufacture of thesecond phase. The water fraction in the second phase is particularly 15wt % or less or 10 wt % or less, especially 7 wt % or less, particularly6 wt % or 5 wt % or less, preferably 2 wt % or less, particularly 1 wt %or less, especially 0.5 wt % or less, particularly 0.1 wt % or 0.05 wt %or less. The specifications in wt % refer to the total weight of thesecond phase.

The at least one second phase comprises at least one polymer. The atleast one polymer is particularly suitable for forming a network.According to the invention, the at least one second phase can have onepolymer, two or more mutually different polymers. In particular, it hasone, two, or more, particularly one or two, preferably one polymer thatis suitable for forming a network. Moreover, the at least one secondphase can have one or more polymers that do not form a network butresult in a thickening and thus to an increasing of the dimensionalstability of the at least one second phase—so-called thickeningpolymers. In a preferred embodiment, the at least one second phase thuscomprises at least one, preferably one polymer for network formation aswell as one or more thickening polymers.

Preferably, the at least one second phase comprises PVA (polyvinylalcohol) and or gelatins as polymers that are suitable for formingnetworks. Furthermore, the at least one second phase preferablycomprises a thickening polymer and particularly polycarboxylate as athickening polymer.

Polyvinyl alcohols are thermoplastic plastics that are manufactured aswhite to yellowish powders, usually through the hydrolysis of polyvinylacetate. Polyvinyl alcohol (PVA) is resistant to almost all water-freeorganic solvents. Polyvinyl alcohols with a molar mass from 30,000 to60,000 g/mol are preferred.

Gelatin is a mixture of substances composed of taste-neutral animalprotein. The main component is denatured or hydrolyzed collagen, whichis produced from the connective tissue of various animal species.Gelatin lacks the essential amino acid tryptophan, so it is notconsidered to be a complete protein. Gelatin swells in water anddissolves when heated starting at about 50° C. When cooled, it forms agel that liquefies again when reheated.

Surprisingly, it was found that PVA and/or gelatin is especially wellsuited to producing second phases that meet the specifications outlinedabove. At least one second phase that has gelatin and/or PVA as well asat least one polyvalent alcohol is therefore especially preferred.Especially preferably, the at least one second phase has gelatin and atleast one polyvalent alcohol. The at least one second phase alsopreferably has PVA and at least one polyvalent alcohol.

According to the invention, the at least one second phase comprises thepolymer that is suitable for forming networks in a fraction of about 5wt % to 40 wt %, particularly 10 wt % to 35 wt %, preferably 15 wt % to20 wt %. Substantially lower fractions of polymer, particularly gelatinand/or PVA, do not result in the formation of a stable gel-like secondphase. Instead, permanent flowing is observed here. Fractions of greaterthan 40 wt % and particularly of greater than 20 wt % result in anextended setting time. The phases remain soft for longer, which resultsin an extended manufacturing process. The values each refer to the totalweight of the second phase.

Especially preferably, the at least one second phase comprises gelatin.Surprisingly, it was found that, with the aid of gelatin, dimensionallystable second phases can be produced within a short curing time. What ismore, the shape and size of phases manufactured in this way remainstable over a long period of time. No size-shrinkage is observed. It hasbeen observed that the quantity of gelatin that must be used varies as afunction of the bloom value. Preferred, the second phase therefore hasgelatin with a bloom value in the range from 60 to 225. The bloom valuedescribes the gel strength or gelling quality of gelatin. Thecharacteristic number is the mass in grams that is required in order fora stamp measuring 0.5 inches in diameter to deform the surface of a6.67% gelatin/water mixture four millimeters deep without breaking it.The experiment is conducted in a standardized manner at exactly 10° C.with previous aging of the gelatin for 17 hours.

If the at least one second phase comprises gelatin having a bloom valueof 150 or greater, particularly from 180 to 225, preferably from 200 to225, then the gelatin fraction with respect to the total weight of thesecond phase is preferably in the range from 10 wt % to 20 wt %,particularly from 15 wt % to 18 wt %. If the bloom value is less than150, particularly from 60 to 120, preferably from 60 to 100, then thegelatin fraction with respect to the total weight of the second phase ispreferably in the range from 15 wt % to 30 wt %, particularly from 20 wt% to 25 wt %. Gelatin with a bloom value of 180 or greater, particularly200 or greater, especially of 225, is preferred. The use of gelatin witha corresponding bloom value enables the viscosity of the second phase tobe controlled well during manufacture. What is more, the quantity ofgelatin required here is less than when gelatins having a lower bloomvalue are used, which can result in a cost reduction.

If the at least one second phase comprises not only gelatin but alsoPVA, the tenacity of the second phase during manufacture is increased.

Surprisingly, it was found that gelatin, together with anionic polymersor copolymer, particularly with sulfopolymers, leads to the formation ofsecond phases with nonsensitive surfaces. Such surfaces can be touchedby an end consumer without having material adhere to his hands. Nor doesany erosion of material occur in packaging. It is therefore preferredthat the second phase contain gelatin and an anionic copolymer/polymer.The anionic polymer fraction is preferably 1 wt % to 35 wt %,particularly 3 wt % to 30 wt %, especially 5 wt % to 25 wt %, preferably5 wt % to 20 wt % with respect to the total weight of the second phase.Sulfopolymers also provide the surface with an outstanding luster. Whatis more, fingerprints are not left behind. The sulfopolymer fraction,particularly the fraction of sulfopolymers with AMPS as the sulfonicacid group-containing monomer, such as Acusol 590, Acusol 588, orSokalan CP50, for example, is therefore preferably 1 wt % to 25 wt %,particularly 3 wt % to 15 wt %, especially 4 wt % to 12 wt %, preferably5 wt % to 10 wt % with respect to the weight of the second phase. In anespecially preferred embodiment, the at least one second phase thereforecomprises gelatin as well as a sulfopolymer and at least one polyvalentalcohol.

According to the invention, the at least one second phase can furthercomprise thickening polymer. This is preferably a polycarboxylate. Acopolymeric polyacrylate, preferably a sulfopolymer, preferably acopolymeric polysulfonate, preferably a hydrophobically modifiedcopolymeric polysulfonate is preferably used as the polycarboxylate. Thecopolymers can have two, three, four, or more different monomer units.Preferred copolymeric polysulfonates contain, besides sulfonic acidgroup-containing monomer(s), at least one monomer from the group of theunsaturated carboxylic acids.

Unsaturated carboxylic acids of the formula R¹(R²)C═C(R³)COOH areespecially preferably used in which R¹ to R³, independently of oneanother, stand for —H, —CH₃, a straight-chain or branched saturatedalkyl residue with 2 to 12 carbon atoms, a straight-chain or branched,mono- or polyunsaturated alkenyl residue with 2 to 12 carbon atoms, with—NH₂, —OH, or —COOH substituted alkyl or alkenyl residues as definedabove, or for —COOH or —COOR⁴, with R⁴ being a saturated or unsaturated,straight-chain or branched hydrocarbon residue with 1 to 12 carbonatoms.

Especially preferred unsaturated carboxylic acids are acrylic acid,methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylicacid, crotonic acid, α-phenylacrylic acid, maleic acid, maleicanhydride, fumaric acid, itaconic acid, citraconic acid,methylenemalonic acid, sorbic acid, cinnamic acid, or mixtures thereof.The unsaturated dicarboxylic acids can obviously also be used.

Among the sulfonic acid group-containing monomers, those of the formulaR⁵(R⁶)C═C(R⁷)—X—SO₃H are preferred in which R⁵ to R⁷, independently ofone another, stand for —H, —CH₃, a straight-chain or branched saturatedalkyl residue with 2 to 12 carbon atoms, a straight-chain or branched,mono- or polyunsaturated alkenyl residue with 2 to 12 carbon atoms, with—NH₂, —OH, or —COOH substituted alkyl or alkenyl residues, or for —COOHor —COOR⁴, with R⁴ being a saturated or unsaturated, straight-chain orbranched hydrocarbon residue with 1 to 12 carbon atoms, and X stands foran optionally present spacer group that is selected from among —(CH₂)n-where n=0 to 4, —COO—(CH₂)k- where k=1 to 6, —C(O)—NH—C(CH₃)₂—,—C(O)—NH—C(CH₃)₂—CH₂—, and —C(O)—NH—CH(CH₃)—CH₂—.

Among these monomers, those of the formulas H₂C═CH—X—SO₃H,H₂C═C(CH₃)—X—SO₃H or H03S—X—(R⁶)C═C(R⁷)—X—SO₃H are preferred in which R⁶and R⁷, independently of one another, are selected from among —H,—CH₂CH₃, —CH₂CH₂CH₃, and —CH(CH₃)₂, and X stands for an optionallypresent spacer group that is selected from among —(CH₂)n- where n=0 to4, —COO—(CH₂)k- where k=1 to 6, —C(O)—NH—C(CH₃)₂—,—C(O)—NH—C(CH₃)₂—CH₂—, and —C(O)—NH—CH(CH₃)—CH₂—.

Especially preferred sulfonic acid group-containing monomers are1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonicacid, 2-acrylamido-2-methyl-1-propanesulfonic acid,2-methacrylamido-2-methyl-1-propanesulfonic acid,3-methacrylamido-2-hydroxy-propanesulfonic acid, allyl sulfonic acid,methallyl sulfonic acid, allyloxybenzene sulfonic acid,methallyloxybenzene sulfonic acid,2-hydroxy-3-(2-propenyloxy)propanesulfonic acid,2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonicacid, 3-sulfopropylacrylate, 3-sulfopropylmethacrylate,sulfomethacrylamide, sulfomethylmethacrylamide, as well as mixtures ofthe above acids or water-soluble salts thereof. In the polymers, thesulfonic acid groups can be present entirely or partially in neutralizedform; that is, the acidic hydrogen atom of the sulfonic acid group canbe exchanged in some or all of the sulfonic acid groups for metal ions,preferably alkali metal ions, and for sodium ions. The use of partiallyor fully neutralized sulfonic acid group-containing copolymers ispreferred according to the invention.

In copolymers that contain only carboxylic acid group-containingmonomers and sulfonic acid group-containing monomers, the monomerdistribution of the copolymers that are preferably used according to theinvention is preferably 5 to 95 wt %; especially preferably, thefraction of sulfonic acid group-containing monomers is 50 to 90 wt %,and the fraction of carboxylic acid group-containing monomers is 10 to50 wt %, with the monomers being preferably selected from among thosementioned above. The molar mass of the sulfo-copolymers that arepreferably used according to the invention can be varied in order toadapt the characteristics of the polymers to the desired use. Preferredcleaning agents are wherein the copolymers have molar masses from 2,000to 200,000 g·mol⁻¹, preferably from 4,000 to 25,000 g·mol⁻¹, andparticularly from 5,000 to 15,000 g·mol⁻¹.

In another preferred embodiment, the copolymers comprise not onlycarboxyl group-containing monomers and sulfonic acid group-containingmonomers but also at least one nonionic, preferably hydrophobic monomer.Particularly, the rinsing performance of dishwashing detergentsaccording to the invention was able to be improved through the use ofthese hydrophobically modified polymers.

Especially preferably, the at least one second phase further comprisesan anionic copolymer, with a copolymer comprising

-   -   i) carboxylic acid group-containing monomers    -   ii) sulfonic acid group-containing monomers    -   iii) nonionic monomers, particularly hydrophobic monomers        being used as the anionic copolymer.

Monomers of the general formula R¹ (R²)C═C(R³)—X—R⁴ are preferably usedas nonionic monomers in which R¹ to R³, independently of one another,stand for —H, —CH₃ or —C₂H₅, X stands for an optionally present spacergroup that is selected from among —CH₂—, —C(O)O— and —C(O)—NH—, and R⁴stands for a straight-chain or branched saturated alkyl residue with 2to 22 carbon atoms or for an unsaturated, preferably aromatic residuewith 6 to 22 carbon atoms.

Especially preferred nonionic monomers are butene, isobutene, pentene,3-methylbutene, 2-methylbutene, cyclopentene, hexene, hexene-1,2-methlypentene-1, 3-methlypentene-1, cyclohexene, methylcyclopentene,cycloheptene, methylcyclohexene, 2,4,4-trimethylpentene-1,2,4,4-trimethylpentene-2,2,3-dimethylhexene-1, 2,4-diemthylhexene-1,2,5-dimethlyhexene-1, 3,5-dimethylhexene-1, 4,4-dimethylhexane-1,ethylcyclohexyn, 1-octene, α-olefins with 10 or more carbon atoms suchas, for example 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene andC₂₂-α-olefin, 2-styrene, α-methyl styrene, 3-methyl styrene, 4-propylstyrene, 4-cyclohexyl styrene, 4-dodecyl styrene,2-ethyl-4-benzylstyrene, 1-vinyl naphthalene, 2-vinyl naphthalene,acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid propylester, acrylic acid butyl ester, acrylic acid pentyl ester, acrylic acidhexyl ester, methacrylic acid methyl ester, N-(methyl)acrylamide,acrylic acid-2-ethylhexyl ester, methacrylic acid-2-ethylhexyl ester,N-(2-ethylhexyl)acrylamide, acrylic acid octyl ester, methacrylic acidoctyl ester, N-(octyl)acrylamide, acrylic acid lauryl ester, methacrylicacid lauryl ester, N-(lauryl)acrylamide, acrylic acid stearyl ester,methacrylic acid stearyl ester, N-(stearyl)acrylamide, acrylic acidbehenyl ester, methacrylic acid behenyl ester, and N-(behenyl)acrylamideor mixtures thereof, particularly acrylic acid, ethyl acrylate,2-acrylamido-2-methylpropane sulfonic acid (AMPS) as well as mixturesthereof.

According to the invention, the at least one second phase can alsocomprise additional polymers, such as PEG, for example, particularlythose polyethylene glycols with an average molar mass between about 200and 8,000, between about 800 and 4,000 g/mol, especially preferably withan average molar mass between 1,000 and 2,000 g/mol, for example around1500 g/mol (INCI: PEG1500), which increase the stability of the secondphase.

The at least one second phase comprises at least one polyvalent alcohol.The at least one polyvalent alcohol enables the manufacture of adimensionally stable, non-flowable second phase within a short settingtime that within 15 minutes or less, particularly 10 minutes or less.Polyvalent alcohols in terms of the present invention are hydrocarbonsin which two, three, or more hydrogen atoms are replaced by OH groups.The OH groups are each bonded to different carbon atoms. No carbon atomhas two OH groups. This is in contrast to (simple) alcohols, in whichonly one hydrogen atom is replaced by an OH group in hydrocarbons.Polyvalent alcohols with two OH groups are referred to as alkanediols,and polyvalent alcohols with three OH groups as alkanetriols. Apolyvalent alcohol thus corresponds to the general formula [KW](OH)_(x),with KW standing for a hydrocarbon that is linear or branched, saturatedor unsaturated, substituted or unsubstituted. A substitution can occurwith —SH or —NH groups, for example. Preferably, KW is a linear orbranched, saturated or unsaturated, unsubstituted hydrocarbon. KWcomprises at least two carbon atoms. The polyvalent alcohol comprises 2,3, or more OH groups (x=2, 3, 4 . . . ), with only one OH group beingbonded to each C atom of the KW. Especially preferably, KW comprises 2to 10—i.e., 2, 3, 4, 5, 6, 7, 8, 9, or 10—carbon atoms. Polyvalentalcohols in which x=2, 3, or 4 can be used in particular (for example,pentaerythritol where x=4). Preferably, x=2 (alkanediol) and/or x=3(alkanetriol).

Especially preferably, the at least one second phase comprises at leastone alkanetriol and/or at least one alkanediol, particularly at leastone C₃ to C₁₀ alkanetriol and/or at least one C₃ to C₁₀ alkanediol,preferably at least one C₃ to C₈ alkanetriol and/or at least one C₃ toC₈ alkanediol, especially at least one C₃ to C₆ alkanetriol and/or atleast one C₃ to C₅ alkanediol as a polyvalent alcohol. Preferably, itcomprises an alkanetriol and an alkanediol as at least one polyvalentalcohol. In a preferred embodiment, the at least second phase thuscomprises at least one polymer, particularly gelatin and/or PVA, as wellas at least one alkanediol and at least one alkanetriol, particularlyone alkanetriol and one alkanediol. A second phase that comprises atleast one polymer, particularly gelatin and/or PVA, as well as a C₃ toC₈ alkanediol and a C₃ to C₈ alkanetriol is also preferred. Alsopreferred is a second phase that comprises at least one polymer,particularly gelatin and/or PVA, as well as a C₃ to C₅ alkanediol and aC₃ to C₆ alkanetriol.

Surprisingly, it was found that, when a suitable triol (alkanetriol) iscombined with a suitable diol (alkanediol), especially short settingtimes can be achieved. What is more, the second phases that are obtainedare transparent and have a shiny surface, which provides for anattractive visual impression of the detergent or cleaning agentaccording to the invention. The terms “diol” and “alkanediol” are usedsynonymously herein. The same applies to “triol” and “alkanetriol.”

According to the invention, the polyvalent alcohols do not comprise anyderivatives thereof, such as ethers, esters, etc.

The quantity of polyvalent alcohol or polyvalent alcohols used in secondphases according to the invention is preferably at least 45 wt %,particularly 55 wt % or more. Preferred quantity ranges are from 5 wt %to 75 wt %, particularly from 10 wt % to 70 wt %, with respect to thetotal weight of the second phase.

Preferably, the C₃- to C₆ alkanetriol is glycerin and/or2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called1,1,1-trimethylolpropane) and/or2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS, tris hydroxymethylaminoethane).

Especially preferably, the C₃- to C₆ alkanetriol is glycerin and/or2-ethyl-2-(hydroxymethyl)-1,3-propanediol (also called1,1,1-trimethylolpropane). The C₃- to C₅ alkanediol is preferably1,3-propanediol and/or 1,2-propanediol. Surprisingly, it was found thatthe chain length of the diol as well as, in particular, the position ofthe OH groups has an influence on the transparency of the second phase.The OH groups of the diol are therefore preferably not arranged onimmediately adjacent C atoms. In particular, three or four carbon atoms,particularly 3 carbon atoms, are located between the two OH groups ofthe diol. Especially preferably, the diol is 1,3-propanediol.Surprisingly, it was found that especially good results are obtainedwith mixtures that comprise glycerin and 1,3-propanediol and/or1,2-propanediol. Especially preferably, the second phase comprisesgelatin, glycerin, and 1,3-propanediol or gelatin,1,1,1-trimethylolpropane and 1,3-propanediol. Here, a dimensionallystable, non-flowable consistency can be achieved within a setting timeof 10 minutes or less and at room temperature that remains dimensionallystable even after an extended storage period. In addition, such a phaseis transparent and has a shiny surface. An especially preferred secondphase therefore comprises gelatin or PVA as a polymer and1,3-propanediol and glycerin or 1,1,1-trimethylolpropane as polyvalentalcohols.

If the second phase comprises an alkanetriol, particularly glycerin or1,1,1-trimethylolpropane, then the fraction of alkanetriol, particularlyglycerin or 1,1,1-trimethylolpropane, is preferably 5 wt % to 70 wt %,particularly 10 wt % to 65 wt %, especially 20 wt % to 40 wt %, withrespect to the total weight of the second phase.

If the second phase optionally comprises several alkanetriol(s), thenthe total fraction of alkanetriol(s) with respect to the total weight ofthe second phase is preferably 5 wt % to 70 wt %, particularly 10 wt %to 65 wt %, especially 20 wt % to 40 wt %.

If glycerin is contained as alkanetriol in the second phase, then thefraction of glycerin with respect to the total weight of the secondphase is preferably 5 wt % to 70 wt %, particularly 10 wt % to 65 wt %,especially 20 wt % to 40 wt %.

If 1,1,1-trimethylolpropane is contained in the second phase, then thefraction of 1,1,1-trimethylolpropane with respect to the total weight ofthe second phase is preferably 5 wt % to 70 wt %, particularly 10 wt %to 65 wt %, especially 20 wt % to 40 wt %. If2-amino-2-hydroxymethyl-1,3-propanediol.

If 2-amino-2-hydroxymethyl-1,3-propanediol is contained in the secondphase, then the fraction of 2-amino-2-hydroxymethyl-1,3-propanediol withrespect to the total weight of the second phase is preferably 5 wt % to70 wt %, particularly 10 wt % to 65 wt %, especially 20 wt % to 40 wt %.

If several alkanediols are optionally contained in the second phase,then the of alkanediols with respect to the total weight of the secondphase is preferably 5 wt % to 70 wt %, particularly 10 wt % to 65 wt %,especially 20 wt % to 40 wt %.

If the second phase comprises an alkanediol, particularly1,3-propanediol, then the fraction alkanediol, particularly1,3-propanediol, with respect to the total weight of the second phase ispreferably 5 wt % to 70 wt %, particularly 10 wt % to 65 wt %,especially 20 wt % to 45 wt %. If 1,3-propanediol is contained in thesecond phase, then the fraction of 1,3-propanediol with respect to thetotal weight of the second phase is preferably 5 wt % to 70 wt %,particularly 10 wt % to 65 wt %, especially 20 wt % to 45 wt %.

A second phase is preferred which contains 20 to 45 wt % 1,3-propanedioland 10 wt % to 65 wt % 2-amino-2-hydroxymethyl-1,3-propanediol, eachwith respect to the total weight of the second phase. A second phase isalso preferred which contains 20 to 45 wt % 1,3-propanediol and 10 wt %to 65 wt % 1,1,1-trimethylolpropane, each with respect to the totalweight of the second phase. A second phase is particularly preferredwhich contains 20 to 45 wt % 1,3-propanediol and 10 wt % to 65 wt %glycerin, each with respect to the total weight of the second phase.

It was found that, in these ranges, a quick setting of a second phase ispossible at 20° C. and yields phases that are storage-stable andtransparent. In particular, the glycerin fraction has an impact on thecuring time.

If the at least one second phase according to the invention has a C₃ toC₆ alkanetriol and a C₃ to C₅ alkanediol, then the weight ratio ispreferably 3:1 to 2:1. In particular, the weight ratio is 2:1 ifglycerin and 1,3-propanediol are contained as polyvalent alcohols.Surprisingly, it was found that, with these weight ratios,storage-stable, shiny, transparent second phases can be obtained withinshort setting times of 10 minutes or less at 20° C.

The detergent or cleaning agent according to the invention preferablycomprises at least one surfactant. This surfactant is selected from thegroup of the anionic, nonionic, and cationic surfactants. The detergentor cleaning agent according to the invention can also contain mixturesof several surfactants that are selected from the same group.

According to the invention, the at least one first phase and the atleast one second phase each contain at least one surfactant. It is alsopossible, however, for only the at least one first phase or only the atleast one second phase to comprise at least one surfactant. If bothphases comprise a surfactant, then they are preferably mutuallydifferent surfactants. It is also possible, however, for the first andsecond phases to have the same surfactant or surfactants. The at leastone first and/or second phases according to the invention preferablycontain at least one nonionic surfactant. All nonionic surfactants thatare known to a person skilled in the art can be used as nonionicsurfactants. Preferably, low-foaming nonionic surfactants are used,particularly alkoxylated, especially ethoxylated, low-foaming nonionicsurfactants. These will be specified in greater detail below.

Suitable nonionic surfactants include alkyl glycosides of the generalformula RO(G)x, for example, in which R corresponds to a primarystraight-chain or methyl-branched aliphatic residue, particularly analiphatic residue that is methyl-branched in the 2 position, with 8 to22, preferably 12 to 18 C atoms, and G is the symbol that stands for aglycose unit with 5 or 6 C atoms, preferably for glucose. The degree ofoligomerization x, which indicates the distribution of monoglycosidesand oligoglycosides, is any number between 1 and 10; preferably, x isfrom 1.2 to 1.4.

Another class of preferred nonionic surfactants, which are used eitheras the sole nonionic surfactant or in combination with other nonionicsurfactants, are alkoxylated, preferably ethoxylated or ethoxylated andpropoxylated fatty acid alkyl esters, preferably with 1 to 4 carbonatoms in the alkyl chain.

Nonionic surfactants of the type of the aminoxides, for exampleN-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and of the fatty acid alkanolamidescan also be suitable. The quantity of these nonionic surfactants ispreferably no more than that of the ethoxylated fatty alcohols,particularly no more than half thereof.

Additional suitable surfactants are the polyhydroxy fatty acid amidesthat are known as PHFAs. Especially preferably, the detergents orcleaning agents according to the invention, particularly cleaning agentsfor dishwashers, contain nonionic surfactants from the group of thealkoxylated alcohols. Nonionic surfactants that are preferably used arealkoxylated, preferably ethoxylated, particularly primary alcohols withpreferably 8 to 18 C atom and, on average, 1 to 12 mols of ethyleneoxide (EO) per mol of alcohol in which the alcohol residue can be linearor preferably methyl-branched in the 2 position, or it can containlinear and methyl-branched residues in admixture, as are usually presentin oxa-alcohol residues. In particular, however, alcohol ethoxylateswith linear residues from alcohols of native origin with 12 to 18 Catoms, for example from coconut, palm, tallow fat, or oleyl alcohol, and2 to 8 EO per mol of alcohol on average are preferred. Examples ofpreferred ethoxylated alcohols are C₁₂₋₁₄ alcohols with 3 EO or 4 EO,C₈₋₁₁ alcohols with 7 EO, C₁₃₋₁₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO,C₁₂₋₁₈ alcohols with 3 EO, 5 EO or 7 EO, and mixtures thereof, such asmixtures of C₁₂₋₁₄ alcohol with 3 EO and C₁₂₋₁₈ alcohol with 5 EO.

Preferred alcohol ethoxylates have a narrowed homolog distribution(narrow range ethoxylates, NRE). In addition to these nonionicsurfactants, fatty alcohols with more than 12 EO can also be used.Examples of these are tallow fatty alcohol fatty alcohols with 14 EO, 25EO, 30 EO, or 40 EO.

Ethoxylated nonionic surfactants are especially preferably used whichwere obtained from C₆₋₂₀ monohydroxy alkanols or C₆₋₂₀ alkyl phenols orC₁₆₋₂₀ fatty alcohols and greater than 12 mols, preferably greater than15 mols, and particularly greater than 20 mols of ethylene oxide per molof alcohol. An especially preferred nonionic surfactant is obtained froma straight-chain fatty alcohol with 16 to 20 carbon atoms (C₁₆₋₂₀alcohol), preferably from a C₁₈ alcohol and at least 12 mols, preferablyat least 15 mols and particularly at least 20 mols of ethylene oxide.Among these, the so-called “narrow-range ethoxylates” are especiallypreferred.

Surfactants that are preferably used originate from the group of thealkoxylated nonionic surfactants, particularly the ethoxylated primaryalcohols and mixtures of these surfactants with structurally complicatedsurfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are alsocharacterized by good foam control.

In relation to the present invention, low-foaming nonionic surfactantshave proven to be especially preferred which have alternating ethyleneoxide and alkylene oxide units. Among these, in turn, surfactants withEO-AO-EO-AO blocks are preferred, with one to ten EO groups and AOgroups being respectively bonded to each other before a block followsfrom the respective other groups. Here, nonionic surfactants of thegeneral formula

are preferred, in which R¹ stands for a straight-chain or branched,saturated or mono- or polyunsaturated C₆₋₂₄ alkyl or alkenyl residue;each R² and R³ group is selected independently of one another from among—CH₃, —CH₂CH₃, —CH₂CH₂—CH₃, —CH(CH₃)₂, and the indices w, x, y, z,independently of one another, stand for integers from 1 to 6.

Preferred nonionic surfactants of the above formula can be producedusing known methods from the corresponding alcohols R¹—OH and ethyleneor alkylene oxide. The R¹ residue in the above formula can varydepending on the origin of the alcohol. If native sources are used, theR¹ residue has an even number of carbon atoms and is generallyunbranched, with the linear residues of alcohols of native origin with12 to 18 C atoms, such as coconut, palm, tallow fat, or oleyl alcohol,for example, being preferred. Some examples of alcohols that areavailable from synthetic sources are the Guerbet alcohols or residuesthat are methyl-branched in the 2 position, or mixtures of residues thatare linear and methyl-branched, such as those usually present inoxa-alcohol residues. Independently of the approach taken in themanufacture of the alcohol used in the nonionic surfactants contained inthe agents, nonionic surfactants are preferred in which R¹ stands for analkyl residue with 6 to 24, preferably 8 to 20, especially preferably 9to 15, and particularly 9 to 11 carbon atoms in the above formula.

Besides propylene oxide, butylene oxide in particular is worthy ofconsideration as an alkylene oxide unit that is contained alternatelywith the ethylene oxide unit in the preferred nonionic surfactants.However, other alkylene oxides in which R² and R³ are selectedindependently of one another from —CH₂CH₂—CH₃ and —CH(CH₃)₂ are alsosuitable. Preferably, nonionic surfactants of the above formula are usedin which R² and R³ stand for a —CH₃ residue, w and x, independently ofone another, stand for values of 3 or 4, and y and z, independently ofone another, stand for values of 1 or 2.

Other nonionic surfactants of the first phase that are preferably usedare nonionic surfactants of the general formulaR¹O(AlkO)_(x)M(OAlk)_(y)OR², where

R¹ and R², independently of one another, stand for a branched orunbranched, saturated or unsaturated, optionally hydroxylated alkylresidue with 4 to 22 carbon atoms; Alk stands for a branched orunbranched alkyl residue with 2 to 4 carbon atoms; x and y,independently of one another, stand for values between 1 and 70; and Mstands for an alkyl residue from the group CH₂, CHR³, CR³R⁴, CH₂CHR³,and CHR³CHR⁴, where R³ and R⁴, independently of one another stand for abranched or unbranched, saturated or unsaturated alkyl residue with 1 to18 carbon atoms.

Nonionic surfactants of the general formulaR¹—CH(OH)CH₂—O(CH₂CH₂O)_(x)(CH₂CHR(OCH₂CH₂)_(y)—CH₂CH(OH)—R² arepreferred,

where R, R¹ and R², independently of one another, stand for an alkylresidue or alkenyl residue with 6 to 22 carbon atoms; x and y,independently of one another, stand for values between 1 and 40.

Compounds of the general formulaR¹—CH(OH)CH₂—O(CH₂CH₂O)_(x)CH₂CHR(OCH₂CH₂)_(y)O—CH₂CH(OH)—R² areparticularly preferred in which R stands for a linear, saturated alkylresidue with 8 to 16 carbon atoms, preferably 10 to 14 carbon atoms, andn and m, independently of one another, have values from 20 to 30. Suchcompounds can be obtained, for example, through the conversion of alkyldiols HO—CHR—CH₂—OH with ethylene oxide, with a conversion with an alkylepoxide being performed subsequently in order to occlude the free OHfunctions under the formation of a dihydroxy ether.

Preferred nonionic surfactants are those of the general formulaR¹—CH(OH)CH₂O-(AO)_(w)-(AO)_(x)-(A″O)_(y)-(A′″O)_(z)—R², in which

-   -   R¹ stands for a straight-chain or branched, saturated or mono-        or polyunsaturated C₆₋₂₄ alkyl or alkenyl residue;    -   R² stands for hydrogen or a linear or branched hydrocarbon        residue with 2 to 26 carbon atoms;    -   A, A′, A″ and A′″, independently of one another, stand for a        residue from the group —CH₂CH₂, —CH₂CH₂—CH₂, —CH₂—CH(CH₃),        —CH₂—CH₂—CH₂—CH₂, —CH₂—CH(CH₃)—CH₂—, —CH₂—CH(CH₂—CH₃);    -   w, x, y and z stand for values between 0.5 and 120, where x, y        and/or z can also be 0.

Through the addition of the abovementioned nonionic surfactants of thegeneral formulaR¹—CH(OH)CH₂O-(AO)_(w)-(A′O)_(x)-(A″O)_(y)-(A′″O)_(z)—R², hereinafteralso called “Hydroxy Mixed Ethers,” the cleaning performance ofpreparations according to the invention can be surprisingly improved,particularly both in comparison to surfactant-free systems and incomparison to systems that contain alternative nonionic surfactants,such as those from the group of the polyalkoxylated fatty alcohols, forexample.

Through the use of these nonionic surfactants with one or more freehydroxyl groups on one or both terminal alkyl residues, the stability ofthe enzymes contained in the cleaning agent preparations according tothe invention can be improved substantially.

In particular, those end-capped poly(alkoxylated) nonionic surfactantsare preferred which, according to the following formula

besides a residue R¹, which stands for linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon residues with 2 to 30carbon atoms, preferably with 4 to 22 carbon atoms, also have a linearor branched, saturated or unsaturated, aliphatic or aromatic hydrocarbonresidue R² with 1 to 30 carbon atoms, where n stands for values between1 and 90, preferably for values between 10 and 80, and particularly forvalues between 20 and 60. Surfactants of the above formula areparticularly preferred in which R¹ stands for C₇ to C₁₃, n stands for awhole natural number from 16 to 28, and R² stands for C₈ to C₁₂.

Surfactants of the formula R¹O[CH₂CH(CH₃)O]_(x)[CH₂CH₂O]_(y)CH₂CH(OH)R²are especially preferred in which R¹ stands for a linear or branchedaliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixturesthereof, R² stands for a linear or branched hydrocarbon residue with 2to 26 carbon atoms or mixtures thereof, x stands for values between 0.5and 1.5, and y stands for a value of at least 15. The group of thesenonionic surfactants includes the C₂₋₂₆ fatty alcohol(PO)₁-(EO)₁₅₋₄₀-2-hydroxyalkyl ethers, particularly including the C₈₋₁₀fatty alcohol (PO)₁-(EO)₂₂-2-hydroxydecyl ethers.

Furthermore, such end-capped poly(alkoxylated) nonionic surfactants ofthe formula R¹O[CH₂CH₂O]_(x)[CH₂CH(R³)O]_(y)CH₂CH(OH)R² are especiallypreferred in which R¹ and R², independently of one another, stand for alinear or branched, saturated or mono- or polyunsaturated hydrocarbonresidue with 2 to 26 carbon atoms, R³, independently of one another, isselected from among —CH₃, —CH₂CH₃, —CH₂CH₂—CH₃, —CH(CH₃)₂ but preferablystands for —CH₃, and x and y, independently of one another, stand forvalues between 1 and 32, with nonionic surfactants in which R³=—CH₃ andhaving values for x from 15 to 32 and for y of 0.5 and 1.5 being veryespecially preferred.

Additional nonionic surfactants that can be preferably used are theend-capped poly(alkoxylated) nonionic surfactants of the formulaR¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR²,

in which R¹ and R² stand for linear or branched, saturated orunsaturated, aliphatic or aromatic hydrocarbon residues with 1 to 30carbon atoms, R³ stands for H or a methyl-, ethyl-, n-propyl-,iso-propyl-, n-butyl-, 2-butyl- or 2-methyl-2-butyl residue, x standsfor values between 1 and 30, and k and j stand for values between 1 and12, preferably between and 5. If the value is x>2, every R³ in the aboveformula R¹O[CH₂CH(R³)O]_(x)[CH₂]_(k)CH(OH)[CH₂]_(j)OR² can be different.R¹ and R² are preferably linear or branched, saturated or unsaturated,aliphatic or aromatic hydrocarbon residues with 6 to 22 carbon atoms,with residues with 8 to 18 C atoms being especially preferred. For theresidue R³, H, —CH₃ or —CH₂CH₃ are especially preferred. Especiallypreferred values for x lie in the range from 1 to 20, particularly from6 to 15.

As described above, every R³ in the above formula can be different ifx>2. In this way, the alkylene oxide unit in the square brackets can bevaried. For example, if x stands for 3, the residue R³ can be selectedin order to form ethylene oxide (R³=H) or propylene oxide (R³=CH₃)units, which can be joined together in any sequence—for example(EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO),and (PO)(PO)(PO). The value 3 has been selected here for the sake ofexample and can by all means be greater, in which case the range ofvariation increases as the values for x increase and includes a largenumber of (EO) groups combined with a small number of (PO) groups, forexample, or vice versa.

Especially preferred end-capped poly(alkoxylated) alcohols of the aboveformula have values of k=1 and j=1, so that the previous formula issimplified to R¹O[CH₂CH(R³)O]_(x)CH₂CH(OH)CH₂OR². In thelatter-mentioned formula, R¹, R², and R³ are as defined above and xstands for numbers from 1 to 30, preferably from 1 to 20, andparticularly from 6 to 18. Surfactants are especially preferred in whichthe residues R¹ and R² have 9 to 14 C atoms, R³ stands for H, and xassumes values from 6 to 15. Ultimately, the nonionic surfactants of thegeneral formula R¹—CH(OH)CH₂O-(AO)_(w)—R² have proven to be especiallyeffective, in which

-   -   R¹ stands for a straight-chain or branched, saturated or mono-        or polyunsaturated C₆₋₂₄ alkyl or alkenyl residue;    -   R² stands for a linear or branched hydrocarbon residue with 2 to        26 carbon atoms;    -   A stands for a residue from the group of CH₂CH₂, CH₂CH₂CH₂,        CH₂CH(CH₃), preferably for CH₂CH₂; and    -   w stands for values between 1 and 120, preferably 10 to 80,        particularly 20 to 40.

The group of these nonionic surfactants includes, for example, the C₄₋₂₂fatty alcohol-(EO)₁₀₋₈₀-2-hydroxyalkyl ethers, particularly includingthe C₈₋₁₂ fatty alcohol-(EO)₂2-2-hydroxydecyl ethers and the C₄₋₂₂ fattyalcohol-(EO)₄₀₋₈₀-2-hydroxyalkyl ethers.

Preferably, the at least one first and/or the at least one second phasecontains at least one nonionic surfactant, preferably a nonionicsurfactant from the group of the Hydroxy Mixed Ethers, with theproportion by weight of the Hydroxy Mixed Ether in the total weight ofthe second phase being preferably 0.5 wt % to 30 wt %, preferably 5 wt %to 25 wt %, and particularly 10 wt % to 20 wt %.

In another preferred embodiment, the nonionic surfactant of the firstand/or second phase is selected from nonionic surfactants of the generalformula R¹—O(CH₂CH₂O)_(x)CR³R⁴(OCH₂CH₂)_(y)0-R², in which R¹ and R²,independently of one another, stand for an alkyl residue or alkylenylresidue with 4 to 22 carbon atoms; R³ and R⁴, independently of oneanother, stand for H or for an alkyl residue or alkenyl residue with 1to 18 carbon atoms, and x and y, independently of one another, stand forvalues between 1 and 40.

Compounds of the general formula R¹—O(CH₂CH₂O)_(x)CR³R⁴(OCH₂CH₂)_(y)O—R²are preferred in which R³ and R⁴ stand for H and the indices x and y,independently of one another, assume values from 1 to 40, preferablyfrom 1 to 15. In particular, compounds of the general formulaR¹—O(CH₂CH₂O)_(x)CR³R⁴(OCH₂CH₂)_(y)O—R² are especially preferred inwhich the residues R¹ and R², independently of one another, representsaturated alkyl residues with 4 to 14 carbon atoms and the indices x andy, independently of one another, assume values from 1 to 15 andparticularly from 1 to 12. In addition, such compounds of the generalformula R¹—O(CH₂CH₂O)_(x)CR³R⁴(OCH₂CH₂)_(y)O—R² are preferred in whichone of the residues R¹ and R² is branched. Compounds of the generalformula R¹—O(CH₂CH₂O)_(x)CR³R⁴(OCH₂CH₂)_(y)O—R² are very especiallypreferred in which the indices x and y, independently of one another,assume values from 8 to 12.

The indicated C chain lengths and degrees of ethoxylation and degrees ofalkoxylation of the nonionic surfactants represent statistical averagesthat can be a whole number or a fraction for a given product. Owing tothe manufacturing methods, commercial products of the abovementionedformulas generally do not consist of an individual representative, butof mixtures, for which reason average values and, resulting from those,fractional numbers can arise both for the C chain lengths and for thedegrees of ethoxylation and degrees of alkoxylation.

As will readily be understood, the aforementioned nonionic surfactants(niosurfactants) can be used not only as individual substances but alsoas surfactant mixtures of two, three, four, or more surfactants.

In the at least one first phase, those nonionic surfactants areparticularly preferred which have a melting point above roomtemperature. Nonionic surfactant(s) with a melting point above 20° C.,preferably above 25° C., especially preferably between 25 and 60° C.,and particularly between 26.6 and 43.3° C. is/are especially preferred.

Suitable nonionic surfactants having melting or softening points in theabovementioned temperature range include low-foaming nonionicsurfactants, for example, which can be solid or highly viscous at roomtemperature. If nonionic surfactants are used which are highly viscousat room temperature, then it is preferred that they have a viscosityabove 20 Pa·s, preferably above 35 Pa·s, and particularly above 40 Pa·s.Nonionic surfactants that have a wax-like consistency at roomtemperature are also preferred.

The nonionic surfactant that is solid at room temperature preferably haspropylene oxide (PO) units in the molecule. Preferably, such PO unitsconstitute up to 25 wt %, especially preferably up to 20 wt %, andparticularly up to 15 wt % of the total molar mass of the nonionicsurfactant. Especially preferred nonionic surfactants are ethoxylatedmonohydroxy alkanols or alkyl phenols that additionally havepolyoxyethylene-polyoxypropylene block copolymer units. The alcohol oralkyl phenol fraction of such nonionic surfactant molecules preferablyconstitutes greater than 30 wt %, especially preferably greater than 50wt %, and particularly greater than 70 wt % of the total molar mass ofsuch nonionic surfactants. Preferred agents are wherein they containethoxylated and propoxylated nonionic surfactants in which the propyleneoxide units in the molecule constitute up to 25 wt %, preferably up to20 wt %, and particularly up to 15 wt % of the total molar mass of thenonionic surfactant.

Additional especially preferred nonionic surfactants to be used in thefirst phase with melting points above room temperature contain 40 to 70%of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymerblend that contains 75 wt % of a reverse block copolymer ofpolyoxyethylene and polyoxypropylene with 17 mols of ethylene oxide and44 mols of propylene oxide and 25 wt % of a block copolymer ofpolyoxyethylene and polyoxypropylene, initiated with trimethylolpropaneand containing 24 mols of ethylene oxide and 99 mols of propylene oxideper mol of trimethylolpropane.

In one preferred embodiment, the proportion by weight of the nonionicsurfactant with respect to the total weight of the first phase is 0.1 to20 wt %, especially preferably 0.5 to 15 wt %, and particularly 2.5 to10 wt %.

All anionic surface-active substances are suitable for use as anionicsurfactants in the dishwashing detergents. These are characterized by awater-solubilizing, anionic group such as a carboxylate, sulfate,sulfonate or phosphate group and a lipophilic alkyl group with about 8to 30 C atoms. In addition, glycol or polyglycol ether groups, ester,ether and amide groups as well as hydroxyl groups can be contained inthe molecule. Suitable anionic surfactants are preferably present in theform of the sodium, potassium and ammonium as well as the mono-, di- andtrialkanol ammonium salts with 2 to 4 C atoms in the alkanol group, butzinc, manganese(II), magnesium, calcium, or mixtures thereof can also beused as the counterion.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ethersulfates, and ether carboxylic acids with 10 to 18 C atoms in the alkylgroup and up to 12 glycol ether groups in the molecule.

Instead of the abovementioned surfactants or in conjunction with them,cationic and/or amphoteric surfactants such as betaines or quaternaryammonium compounds can also be used. It is preferred, however, that nocationic and/or amphoteric surfactants be used.

Surfactants influence the opacity of the second phase. In a likewisepreferred, different embodiment, the second phase is therefore free ofsurfactants, particularly of nonionic surfactants.

Preferred detergent or cleaning agents according to the invention arealso wherein, in the at least one first and/or the at least one secondphase, particularly in the first phase, they contain less than 1.0 wt %and particularly no anionic surfactant, since the addition of anionicsurfactants has proven disadvantageous with respect to the phasecharacteristics, particularly the hardness, friability (wearingcharacteristics), and resetting characteristics.

Substances that are also used as ingredients of cosmetic agents are alsodesignated in the following according to the International Nomenclatureof Cosmetic Ingredients (INCI) as appropriate. Chemical compounds bearan INCI designation in English. The INCI designations can be found inthe “International Cosmetic lngredient Dictionary and Handbook, 7thEdition (1997),” which is published by The Cosmetic, Toiletry andFragrance Association (CTFA), Washington D.C. (USA). The expression CASmeans that the following numerical sequence is a designation of theChemical Abstracts Service.

Besides the surfactants, the at least one second phase can also containsugars. According to the invention, sugars include monosaccharides,disaccharides, and oligosaccharides. Preferably, the second phasecomprises disaccharides, particularly sucrose. The sucrose fraction is 0wt % to 30 wt %, particularly 5 wt % to 25 wt %, especially preferably10 wt % to 20 wt %, with respect to the weight of the second phase. Ingreater quantities, the sugar does not dissolve completely in the secondphase and results in the clouding thereof. Through the use of sugar,particularly in a proportion of 10 wt % to 15 wt %, the development ofmoisture is reduced and the adhesion to the at least one first phasethus improved.

The use of builder substances (builders) such as silicates, aluminumsilicates (particularly zeolites), salts of organic di- andpolycarboxylic acids, as well as mixtures of these substances,preferably water-soluble builder substances, can be advantageous.

In an embodiment that is preferred according to the invention, the useof phosphates (including polyphosphates) is omitted either largely orcompletely. In this embodiment, the agent preferably contains less than5 wt %, especially preferably less than 3 wt %, particularly less than 1wt % phosphate(s). Especially preferably, the agent in this embodimentis completely phosphate-free, i.e., the agents contain less than 0.1 wt% phosphate(s).

The builders include, in particular, carbonates, citrates, phosphonates,organic builders, and silicates. The proportion by weight of the totalbuilders with respect to the total weight of agents according to theinvention is preferably 15 to 80 wt % and particularly 20 to 70 wt %.

Some examples of organic builders that are suitable according to theinvention are the polycarboxylic acids (polycarboxylates) that can beused in the form of their sodium salts, with polycarboxylic acids beingunderstood as being those carboxylic acids that carry more than one,particularly two to eight acid functions, preferably two to six,particularly two, three, four, or five acid functions in the entiremolecule. As polycarboxylic acids, dicarboxylic acids, tricarboxylicacids, tetracarboxylic acids, and pentacarboxylic acids, particularlydi-, tri-, and tetracarboxylic acids, are thus preferred. Thepolycarboxylic acids can also carry additional functional groups such ashydroxyl or amino groups, for example. For example, these include citricacid, adipic acid, succinic acid, glutaric acid, malic acid, tartaricacid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids,for example galactaric acid and glucaric acid), aminocarboxylic acid,particularly aminodicarboxylic acids, aminotricarboxylic acids,aminotetracarboxylic acids such as, for example, nitrilotriacetic acid(NTA), glutamic-N,N-diacetic acid (also calledN,N-bis(carboxymethyl)-L-glutamic acid or GLDA), methyl glycine diaceticacid (MGDA) and derivatives thereof and mixtures thereof. Preferredsalts are the salts of the polycarboxylic acids such as citric acid,adipic acid, succinic acid, glutaric acid, tartaric acid, GLDA, MGDA,and mixtures thereof.

Other substances that are suitable as organic builders are polymericpolycarboxylates (organic polymers with a plurality of (particularlygreater than ten) carboxylate functions in the macromolecule),polyaspartates, polyacetals, and dextrins.

Besides their building effect, the free acids also typically have thequality of an acidifying component. Particularly noteworthy here arecitric acid, succinic acid, glutaric acid, adipic acid, gluconic acid,and any and all mixtures thereof.

Especially preferred detergents or cleaning agents according to theinvention, particularly dishwashing detergents, preferably dishwashingdetergents for dishwashers, contain one or more salts of the citricacid, i.e., citrates, as one of their essential builders. These arepreferably contained in a proportion of 2 to 40 wt %, particularly 5 to30 wt %, especially 7 to 28 wt %, especially preferably 10 to 25 wt %,very especially preferably 15 to 20 wt %, each with respect to the totalweight of the agent.

It is also especially preferred to use carbonate(s) and/or hydrogencarbonate(s), preferably alkali carbonate(s), especially preferablysodium carbonate (soda), in quantities of 2 to 50, preferably 4 to 40 wt%, and particularly 10 to 30 wt %, very especially preferably 10 to 24wt %, each with respect to the weight of the agent.

Especially preferred detergents or cleaning agents according to theinvention, particularly dishwashing detergents, preferably dishwashingdetergents for dishwashers, are wherein they contain at least twobuilders from the group of the silicates, phosphonates, carbonates,aminocarboxylic acids, and citrates, with the proportion by weight ofthese builders with respect to the total weight of the cleaning agentaccording to the invention being preferably 5 to 70 wt %, morepreferably 15 to 60 wt %, and particularly 20 to 50 wt %. Thecombination of two or more builders from the abovementioned group hasproven advantageous for the cleaning and rinsing of detergents orcleaning agents according to the invention, particularly dishwashingdetergents, preferably dishwashing detergents for dishwashers. Beyondthe builders mentioned here, one or more other builders can beadditionally contained.

Preferred detergents or cleaning agents, preferably dishwashingdetergents, preferably dishwashing detergents for dishwashers, arecharacterized by a builder combination of citrate and carbonate and/orhydrogen carbonate. In one embodiment that is very especially preferredaccording to the invention, a mixture of carbonate and citrate is usedin which the quantity of carbonate is preferably 5 to 40 wt %,particularly 10 to 25 wt %, and the quantity of citrate is preferably 5to 35 wt %, particularly 10 to 25 wt %, very especially preferably 15 to20 wt %, each with respect to the total quantity of the cleaning agent,with the total quantity of these two builders preferably being 20 to 65wt %, particularly 25 to 60 wt %, more preferably 30 to 50 wt %.Moreover, one or more other builders can be additionally contained.

The detergents or cleaning agents according to the invention,particularly dishwashing detergents, preferably dishwashing detergentsfor dishwashers, can contain phosphonates in particular as an additionalbuilder. A hydroxy alkane and/or amino alkane phosphonate is preferablyused as a phosphonate compound. Among the hydroxy alkane phosphonates,1-hydroxyethane-1,1-diphosphonate (HEDP) has special significance.Ethylenediamine tetramethylene phosphonate (EDTMP), diethylenetriaminepentamethylene phosphonate (DTPMP) and higher homologs thereof arepreferably considered. Phosphonates are preferably contained in theagents according to the invention in quantities from 0.1 to 10 wt %,particularly in quantities from 0.5 to 8 wt %, very especiallypreferably from 2.5 to 7.5 wt %, each with respect to the total weightof the agent.

The combined use of citrate, (hydrogen) carbonate, and phosphonate isespecially preferred. These can be used in the abovementionedquantities. In particular, quantities of 10 to 25 wt % citrate, 10 to 30wt % carbonate (or hydrogen carbonate), and 2.5 to 7.5 wt % phosphonateare used, each with respect to the total weight of the agent.

Additional especially preferred detergents or cleaning agents,particularly dishwashing detergents, preferably dishwashing detergentsfor dishwashers, are wherein, in addition to citrate and (hydrogen)carbonate and, optionally, phosphonate, they contain an additionalphosphorous-free builder. In particular, it is selected from among theaminocarboxylic acids, with the additional phosphorous-free builderpreferably being selected from among methyl glycine diacetic acid(MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA),hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS), andethylenediamine disuccinate (EDDS), especially preferably from amongMGDA or GLDA. An example of an especially preferred combination iscitrate, (hydrogen) carbonate, and MGDA as well as, optionally,phosphonate.

The proportion by weight of the additional phosphorous-free builder,particularly of the MGDA and/or GLDA, is preferably 0 to 40 wt %,particularly 5 to 30 wt %, especially 7 to 25 wt %. The use of MGDA orGLDA, particularly MGDA, as a granulate is especially preferred.Advantageous in this regard are MGDA granulates that contain as littlewater as possible and/or have a lower hygroscopicity (water absorptionat 25° C., normal pressure) than non-granulated powders. The combinationof at least three, particularly at least four builders from theabovementioned group has proven advantageous for the cleaning andrinsing of cleaning agents according to the invention, particularlydishwashing detergents, preferably dishwashing detergents fordishwashers. Besides those, additional builders can also be contained.

Polymeric polycarboxylates are still suitable as organic builders; theseinclude the alkali metal salts of polyacrylic acid or of polymethacrylicacid, for example those having a relative molecular mass of 500 to70,000 g/mol. Suitable polymers are particularly polyacrylates, whichpreferably have a molecular mass from 1,000 to 20,000 g/mol. Due totheir superior solubility, the short-chain polyacrylates, which havemolar masses from 1,100 to 10,000 g/mol, and especially preferably from1,200 to 5,000 g/mol, can be preferred from this group.

The (homo)polymeric polycarboxylates contained in the detergents orcleaning agents according to the invention, particularly dishwashingdetergents, particularly dishwashing detergents for dishwashers, ispreferably 0.5 to 20 wt %, more preferably 2 to 15 wt %, andparticularly 4 to 10 wt %.

Detergents or cleaning agents according to the invention, particularlydishwashing detergents, particularly dishwashing detergents fordishwashers, can also contain, as a builder, crystalline layeredsilicates of the general formula NaMSi_(x)O_(2x+1).y H₂O, where Mrepresents sodium or hydrogen, x is a number from 1.9 to 22, preferablyfrom 1.9 to 4, with 2, 3, or 4 being especially preferred values for x,and y stands for a number from 0 to 33, preferably from 0 to 20.Amorphous sodium silicates with an Na₂O:SiO₂ modulus of 1:2 to 1:3.3,preferably 1:2 to 1:2.8, and particularly 1:2 to 1:2.6 can also be usedwhich preferably have retarded dissolution and secondary washingproperties.

In certain detergents or cleaning agents according to the invention,particularly dishwashing detergents, particularly dishwashing detergentsfor dishwashers, the silicate content in relation to the total weight ofthe detergent or cleaning agent is limited to quantities below 10 wt %,preferably below 5 wt %, and particularly below 2 wt %.

In supplementation to the aforementioned builders, the detergents orcleaning agents according to the invention can also contain alkali metalhydroxides. These alkali carriers are preferably used in the detergentsor cleaning agents and particularly in the at least one second phaseonly in small quantities, preferably in quantities below 10 wt %,preferably below 6 wt %, more preferably below 5 wt %, especiallypreferably between 0.1 and 5 wt %, and particularly between 0.5 and 5 wt%, each with respect to the total weight of the detergent or cleaningagent. Alternative detergents or cleaning agents according to theinvention are free of alkali metal hydroxides.

As an additional component, cleaning agents according to the inventionpreferably contain enzyme(s) in the at least one first and/or secondphase. These include, in particular, proteases, amylases, lipases,hemicellulases, cellulases, perhydrolases, or oxidoreductases, as wellas, preferably, mixtures thereof. In principle, these enzymes are ofnatural origin; starting from the natural molecules, improved variantsfor use in cleaning agents are available which are preferably usedaccordingly. Cleaning agents according to the invention preferablycontain enzymes in total quantities from 1×10⁻⁶ wt % to 5 wt % withrespect to active protein. The protein concentration can be determinedwith the aid of known methods, for example the BCA method or the Biuretmethod.

Among the proteases, the subtilisin-type proteases are preferred.Examples of these are the subtilisins BPN′ and Carlsberg, as well as thefurther-developed forms thereof, protease PB92, subtilisins 147 and 309,the alkaline protease from Bacillus lentus, subtilisin DY, but not theenzymes thermitase, proteinase K and proteases TW3 and TW7, which belongto the subtilases but no longer to the subtilisins in the narrowersense.

Examples of amylases that can be used according to the invention areα-amylases from Bacillus licheniformis, from B. amyloliquefaciens, fromB. stearothermophilus, from Aspergillus niger, and A. oryzae, as well asthe further developments of the abovementioned amylases that have beenimproved for use in cleaning agents. Others that are particularlynoteworthy for this purpose are the α-amylases from Bacillus sp. A 7-7(DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B.agaradherens (DSM 9948).

Furthermore, lipases or cutinases can be used according to theinvention, particularly due to their triglyceride-cleaving activities,but also in order to produce peracids in situ from suitable precursors.These include, for example, the lipases that could originally beobtained from Humicola lanuginosa (Thermomyces lanuginosus) and thosethat have been further developed, particularly those with the amino acidexchange in positions D96LT213R and/or N233R, especially preferably allof the exchanges D96L, T213R, and N233R.

Moreover, enzymes can be used which can be grouped together under theterm “hemicellulases.” These include, for example, mannanases, xanthanlyases, pectin lyases (=pectinases), pectinesterases, pectate lyases,xyloglucanases (=xylases), pullulanases, and β-glucanases.

In order to increase the bleaching effect, oxidoreductases such asoxidases, oxygenases, catalases, peroxidases such as halo-, chloro-,bromo-, lignin, glucose, or manganese peroxidases, dioxygenases orlaccases (phenoloxidases, polyphenoloxidases) can be employed accordingto the invention. Advantageously, organic, especially preferablyaromatic compounds that interact with the enzymes are additionally addedin order to potentiate the activity of the relevant oxidoreductases(enhancers) or, in the event of greatly differing redox potentials, toensure the flow of electrons between the oxidizing enzymes and thecontaminants (mediators). A protein and/or enzyme can be protected,especially during storage, against damage, for example in the forminactivation, denaturing, or decomposition caused, for example, byphysical influences, oxidation, or proteolytic cleavage. When theproteins and/or enzymes are obtained microbially, it is especiallypreferred that proteolysis be inhibited, particularly if the agents alsocontain proteases. To this end, cleaning agents can contain stabilizers;the provision of such agents constitutes a preferred embodiment of thepresent invention.

Proteases and amylases that are active in detergency are generally notmade available in the form of the pure protein, but rather in the formof stabilized, storable and transportable preparations. These ready-madepreparations include, for example, the solid preparations obtainedthrough granulation, extrusion, or lyophilization or, particularly inthe case of liquid of gel-type agents, solutions of the enzymes,advantageously maximally concentrated, low-moisture, and/or supplementedwith stabilizers or other adjuvants.

Alternatively the enzymes can also be encapsulated for the at least onefirst and/or the at least one second phase, for example throughspray-drying or extrusion of the enzyme solution together with apreferably natural polymer or in the form of capsules, for example thosein which the enzymes are enclosed in a set gel, or in those of thecore-shell type in which an enzyme-containing core is coated with awater-, air-, and/or chemical-impermeable protective layer. In the caseof overlaid layers, other active substances, such as stabilizers,emulsifiers, pigments, bleaching agents, or dyes, can be additionallyapplied. Such capsules are applied using inherently known methods, forexample through shaking or roll granulation or in fluidized bedprocesses. Such granulates are advantageously low in dust, for exampledue to the application of polymeric film-formers, and stable in storagedue to the coating.

Moreover, it is possible to formulate two or more enzymes together, sothat a single granulate has several enzyme activities.

As can be seen from the preceding remarks, the enzyme protein forms onlya fraction of the total weight of conventional enzyme preparations.Protease and amylase preparations that are preferably used according tothe invention contain between 0.1 and 40 wt %, preferably between 0.2and 30 wt %, especially preferably between 0.4 and 20 wt %, andparticularly between 0.8 and 10 wt % of the enzyme protein. Inparticular, those cleaning agents are preferred which contain, withrespect to their total weight, 0.1 to 12 wt %, preferably 0.2 to 10 wt%, and particularly 0.5 to 10 wt % of the respective enzyme preparation.

Besides to the components cited in the foregoing, the at least one firstand/or the at least one second phase of the detergent or cleaning agentaccording to the invention can contain additional ingredients. Forexample, these include anionic, cationic, and/or amphoteric surfactants,bleaching agents, bleach activators, bleach catalysts, other solvents,thickeners, sequestering agents, electrolytes, corrosion inhibitors,particularly silver anti-tarnishing agents, glass corrosion inhibitors,foam inhibitors, dyes, aromas (particularly in the at least one phase),additives for improving the flow and drying behavior, for adjusting theviscosity, for stabilization, UV stabilizers, Perglanzmittel (INCIOpacifying Agents; for example, glycol distearate, such as Cutina® AGSby Cognis, or mixtures containing same, such as Euperlane® by Cognis),preservatives (for example, the technical preservative2-bromo-2-nitropropane-1,3-diol, which is also known as Bronopol (CAS52-51-7) and is commercially available as Myacide® BT or as BootsBronopol BT from the Boots company), antimicrobial agents(disinfectants), and pH adjusters in quantities of usually no more than5 wt %.

Agents according to the invention preferably contain at least onealkanolamine as an additional solvent. The alkanolamine is preferablyselected from the group consisting of mono-, di-, triethanol- andpropanolamine and mixtures thereof. The alkanolamine is preferablycontained in agents according to the invention in a quantity of 0.5 to10 wt %, particularly in a quantity of 1 to 6 wt %. In a preferreddetergent or cleaning agent, the at least one second phase is free ofalkanolamine, and the alkanolamine is contained only in the at least onefirst phase.

In a preferred embodiment, detergents or cleaning agents according tothe invention, particularly dishwashing detergents, contain, as anadditional component, at least one zinc salt as a glass corrosioninhibitor. The zinc salt can be an inorganic or organic zinc salt. Thezinc salt to be used according to the invention preferably has asolubility in water of greater than 100 mg/l, preferably greater than500 mg/l, especially preferably greater than 1 g/l, and particularlygreater than 5 g/l (all solubilities at 20° C. water temperature). Theinorganic zinc salt is preferably selected from the group consisting ofzinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zincsulfate. The organic zinc salt is preferably selected from the groupconsisting of zinc salts of monomeric or polymeric organic acids,particularly from the group of zinc acetate, zinc acetyl acetonate, zincbenzoate, zinc formiate, zinc lactate, zinc gluconate, zinc ricinoleate,zinc abietate, zinc valerate, and zinc-p-toluene sulfonate. In anembodiment that is especially preferred according to the invention, zincacetate is used as a zinc salt. The zinc salt is preferably contained incleaning agents according to the invention in a quantity of 0.01 wt % to5 wt %, especially preferably in a quantity of 0.05 wt % to 3 wt %,particularly in a quantity of 0.1 wt % to 2 wt %, with respect to thetotal weight of the cleaning agent. In addition or alternatively to theabovementioned salts (particularly the zinc salts), polyethyleniminessuch as those which are available under the name Lupasol® (BASF) arepreferably used as glass corrosion inhibitors in a quantity of 0 to 5 wt%, particularly 0.01 to 2 wt %.

Polymers that are suitable as additives are particularly maleic acidacrylic acid copolymer Na salt (for example, Sokalan® CP 5 by BASF,Ludwigshafen (Germany)), modified polyacrylic acid Na salt (for example,Sokalan® CP 10 by BASF, Ludwigshafen (Germany)), modifiedpolycarboxylate Na salt (for example, Sokalan® HP 25 by BASF,Ludwigshafen (Germany)), polyalkylene oxide, modifiedheptamethyltrisiloxane (for example, Silwet® L-77 by BASF, Ludwigshafen(Germany)), polyalkylene oxide, modified heptamethyltrisiloxane (forexample, Silwet® L-7608 by BASF, Ludwigshafen (Germany)), as well aspolyethersiloxane (copolymers of polymethyl siloxanes with ethyleneoxide/propylene oxide segments (polyether blocks)), preferablywater-soluble, linear polyether siloxanes with terminal polyetherblocks, such as Tegopren® 5840, Tegopren® 5843, Tegopren® 5847,Tegopren® 5851, Tegopren® 5863, or Tegopren® 5878 by Evonik, Essen(Germany). Builder substances that are suitable as additives areparticularly polyaspartic acid Na salt, ethylenediamine triacetatecocoalkyl acetamide (for example, Rewopol® CHT 12 by Evonik, Essen(Germany)), methyl glycine diacetic acid tri-Na salt, andacetophosphonic acid. In the case of Tegopren® 5843 and Tegopren® 5863,mixtures with surface-active or polymeric additives exhibit synergisms.However, the use of Tegopren types 5843 and 5863 on hard surfaces madeof glass, particularly glass dishes, is less preferred, since thesesilicone surfactants can adhere to glass. In a special embodiment of theinvention, the abovementioned additives are omitted.

A preferred detergent or cleaning agent, particularly dishwashingdetergent, preferably also comprises a bleaching agent, particularly anoxygen bleaching agent, as well as, optionally, a bleach activatorand/or bleach catalyst. Insofar as they are present, they are containedexclusively in the first phase.

As a preferred bleaching agent, cleaning agents according to theinvention contain an oxygen bleaching agent from the group of sodiumpercarbonate, sodium perborate tetrahydrate, and sodium perboratemonohydrate. Some other examples of bleaching agents that can be usedare peroxypyrophosphates, citrate perhydrates, and H₂O₂-yieldingperacidic salts or peracids, such as perbenzoates, peroxophthalates,diperazelaic acid, phthaloimino peracid, or diperdodecane diacid.Moreover, bleaching agents from the group of the organic bleachingagents can also be used. Typical organic bleaching agents are the diacylperoxides, such as dibenzoyl peroxide, for example. Other typicalorganic bleaching agents are the peroxy acids, with the alkylperoxyacids and the arylperoxy acids meriting special mention as examples. Dueto its good bleaching performance, sodium percarbonate is especiallypreferred. One especially preferred oxygen bleaching agent is sodiumpercarbonate.

Compounds which, under perhydrolysis conditions, yield aliphaticperoxocarboxylic acids with preferably 1 to 10 C atoms, particularly 2to 4 C atoms, and/or optionally substituted perbenzoic acid, can be usedas bleach activators. Substances that carry the O- and/or N-acyl groupof the cited number of C atoms and/or optionally substituted benzoylgroups are suitable. Multiply acylated alkylene diamines are preferred,with tetraacetylethyl ethylenediamine (TAED) having proven to beespecially suitable.

The bleach catalysts are bleach-boosting transition metal salts ortransition metal complexes such as, for example, Mn-, Fe-, Co-, Ru-, orMo-salene complexes or -carbonyl complexes. Mn-, Fe-, Co-, Ru-, Mo-,Ti-, V-, and Cu-complexes with N-containing tripod ligands as well asCo-, Fe- Cu-, and Ru-ammine complexes can be used as bleach catalysts.Complexes of manganese in oxidation stage II, III, IV, or IV areespecially preferably used which preferably contain one or moremacrocyclic ligands with the donor functions N, NR, PR, O and/or S.Preferably, ligands are used which have nitrogen donor functions. It isespecially preferred to use bleach catalyst or catalysis in the agentsaccording to the invention which contains or contain, as amacromolecular ligand, 1,4,7-trimethyl-1,4,7-triazacyclononane(Me-TACN), 1,4,7-triazacyclononane (TACN),1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD),2-methyl-1-1,4,7-trimethyl-1,4, 7-triazacyclononane (Me/Me-TACN), and/or2-methyl-1,4,7-triazacyclononane (Me/TACN). Some examples of suitablemanganese complexes are [Mn^(III) ₂(μ-O)1(μ-OAc)₂(TACN)₂](ClO₄)₂,[Mn^(III)Mn^(IV)(μ-O)₂(μ-OAc)₁(TACN)₂](BPh₄)₂, [Mn^(IV)₄(μ-O)₆(TACN)₄](ClO₄)₄, [Mn^(III) ₂(μ-O)₁(μ-OAc)₂(Me-TACN)₂](CIO₄)₂,[Mn^(III)Mn^(IV)(μ-O)₁(μ-OAc)₂(Me-TACN)₂](CIO₄)₃, [Mn^(IV)₂(μ-O)₃(Me-TACN)₂](PFs)₂, and [Mn^(IV) ₂(μ-O)₃(Me/Me-TACN)₂](PFs)₂(where OAc═OC(O)CH₃).

When benzoic acid, salicylic acid, or lactic acid are used as pHregulators and/or buffer substances, these compounds can support orboost the antibacterial effect of the silver and/or of the silvercompound.

The detergent or cleaning agent according to the invention comprises atleast one first phase (1) and at least one second phase (2). Thedetergent or cleaning agent can thus have one, two, three, or moremutually different first phases (1); likeside, it can have one, two,three, or more mutually different second phases (2). Preferably, thedetergent or cleaning agent according to the invention comprises onefirst phase (1) and one second phase (2). Especially preferably, thedetergent or cleaning agent comprises two first phases (1) and onesecond phase (2). Preferably, it comprises two first phases (1) and twosecond phases (2). An embodiment is also preferred in which thedetergent or cleaning agent comprises three first phases (1) and one ortwo second phases (2). The weight ratio of the at least one first phase(1) to the at least one second phase (2) is preferably 20:1 to 8:1. Thetotal weight of phase (1) in a cleaning agent portion can be between 8and 30 g, particularly 10 to 25 g, preferably 12 to 21 g, for example 14to 19 g. This weight ratio provides a good concentration of therespective ingredients of the first (1) and second phase (2) in acleaning procedure.

According to the invention, the at least one first phase (1) and the atleast one second phase (2) are adjacent to one another over all or partof their surfaces. It is preferred in this regard that the two phases beimmediately adjacent. It is possible, however, for the at least onefirst phase (1) or the at least one second phase (2) or the at least onefirst phase (1) and the at least one second phase (2) to be enclosed ina water-soluble film or contained in a water-soluble pouch. Preferably,the entire agent is contained in a water-soluble pouch or, especiallypreferably, enclosed by a water-soluble film.

If the at least one first phase (1) and the at least one second phase(2) are directly adjacent to one another over all or part of theirsurfaces, stability is important, as is a setting time of the at leastone second phase (2) that is as short as possible. Here, stability meansthat components contained in the second phase do not cross over into theat least one first phase, but rather the at least one first phase andthe at least one second phase remain visually separate from one anothereven after a long period of storage and do not interact with each other,for example through the diffusion of liquid components from one phase tothe other or the reaction of components of one phase with those in theother phase, or loss of adhesion of the second phase (2) to theparticularly pressed, compacted first phase (1) as a result of theleakage of liquid. Surprisingly, it was found that this can be madepossible by a second phase that has glycerin, gelatin, and at least oneC₃ to C₅ alkanediol.

The water-soluble film or the water-soluble pouch preferably comprises awater-soluble polymer. Some preferred water-soluble polymers that arepreferably used as water-soluble packaging are polyvinyl alcohols,acetalized polyvinyl alcohols, polyvinyl pyrrolidones, polyethyleneoxides, celluloses, and gelatin, with polyvinyl alcohols and acetalizedpolyvinyl alcohols being especially preferably used.

“Polyvinyl alcohols” (abbreviated as PVAL, and occasionally as PVOH) isthe designation for polymer having the general structure

which also contain structural units in small proportions (about 2%) ofthe type

Commercially available polyvinyl alcohols, which are offered as awhite-yellowish powder or granulate with degrees of polymerization inthe range from about 100 to 2,500 (molar masses from about 4,000 to100,000 g/mol) have degrees of hydrolysis of 87-99 mol %, so they stillcontain residual acetyl groups.

In the framework of the present invention, it is preferred if thewater-soluble packaging comprises at least some proportion of polyvinylalcohol whose degree of hydrolysis is preferably 70 to 100 mol %,particularly 80 to 90 mol %, especially preferably 81 to 89 mol %, andabove all 82 to 88 mol %. In a preferred embodiment, the water-solublepackaging consists of at least 20 wt %, especially preferably at least40 wt %, very especially preferably at least 60 wt %, and particularlyat least 80 wt % of a polyvinyl alcohol whose degree of hydrolysis is 70to 100 mol %, preferably 80 to 90 mol %, especially preferably 81 to 89mol %, and particularly 82 to 88 mol %.

Preferably, polyvinyl alcohols are used as materials for the packagingwhich lie within a defined range of molecular weights, with it beingpreferred according to the invention that the packaging materialcomprise a polyvinyl alcohol whose molecular weight lies in the rangefrom 5,000 g·mol⁻¹ to 100,000 g·mol⁻¹, preferably from 10,000 g·mol⁻¹ to90,000 g·mol⁻¹, especially preferably from 12,000 g·mol⁻¹ to 80,000g·mol⁻¹, and particularly from 15,000 g·mol⁻¹ to 70,000 g·mol⁻¹.

The degree of polymerization of such preferred polyvinyl alcohols isfrom about 200 to about 2,100, preferably from about 220 to about 1890,especially preferably between about 240 to about 1680, and particularlybetween about 260 to about 1500.

The water solubility of polyvinyl alcohol can be altered throughpost-treatment with aldehydes (acetalization) or ketones (ketalization).Especially preferred and, due to their decidedly good solubility in coldwater, especially advantageous polyvinyl alcohols have been producedwhich can be acetalized or ketalized with the aldehyde or keto groups ofsaccharides or polysaccharides or mixtures thereof. It is extremelyadvantageous to use the reaction products from polyvinyl alcohol andstarch. Furthermore, the water solubility can be altered and thus set atdesired values in a targeted manner using Ni or Cu salts or throughtreatment with dichromates, boric acid, or borax.

The water-soluble pouch preferably has a thickness of 10 μm to 500 μm,particularly 20 μm to 400 μm, especially preferably 30 μm to 300 μm,above all 40 μm to 200 μm, particularly 50 μm to 150 μm. One polyvinylalcohol that is especially preferably used is available under the tradename M8630 (Monosol), for example.

The water-soluble film that is preferably used in the narrow coveringespecially preferably comprises polyvinyl alcohol as described above,with a thickness of 10 μm to 100 μm, particularly 12 μm to 60 μm,especially preferably 15 μm to 50 μm, above all 20 μm to 40 μm,particularly 22 μm to 35 μm being preferably used as an initialthickness.

In the case of a narrow covering, a single-use portion of the detergentor cleaning agent is enclosed in each. For the covered detergents orcleaning agents according to the invention, it is important that thecovering rest tightly against the entire surface of the tablets.

Ideally, the covering is even under tension, which is not absolutelynecessary, however. This tight abutment of the covering is conducive todisintegration: Upon initial contact with water, the covering will allowa small quantity of water through at some place and does not have todissolve at all initially. It is there that the disintegrant containedin the tablet begins to swell. As a result, the covering now tears opensuddenly due to the increase in volume and releases the tablet. In thecase of a covering that does not abut tightly, the mechanism beingdescribed here does not work, since the tablet can swell withoutbreaking the covering open. The use of a swellable disintegration aid issuperior to a gas-producing system, since its bursting effect alwaysresults in the tearing-open of the covering. In a gas-producing system,the bursting effect can “fizzle out” due to the leakage of the gas fromthe leak point.

Single-use portions of detergents or cleaning agents according to theinvention are wherein the clearance between the single-use portion andwater-soluble covering over the entire surface is 0.1 to 1000 μm,preferably 0.5 to 500 μm, especially preferably 1 to 250 μm, andparticularly 2.5 to 100 μm.

In a preferred embodiment, the film covering is first placed and weldedloosely around a single-use portion of detergent or cleaning agent andthen shrunk onto same, thus resulting in close contact between the filmpackaging and the cleaning agent concentrate. Consequently, single-useportions of detergent or cleaning agent according to the invention arewherein the covering is a film packaging that is shrunk onto same.

For example, this encasement can be achieved by placing a water-solublebase film onto a transport chain or a shaping tool, upon which one ormore portions of detergent or cleaning agent are placed onto the basefilm; a water-soluble top film is then placed onto the portion(s) ofdetergent or cleaning agent, and this is then fixed to the base filmunder the inclusion of the portion of detergent or cleaning agent.Alternatively, this step can also be performed using a single-strandedfilm that is then placed around the single-use portions as a tube. Thefilms are then sealed and, optionally, cut. The film can then be shrunkthrough the use of hot air or infrared radiation, optionally withpressing force.

Such water-soluble coverings have also already been described in patentapplications WO 2004/031338 A and WO 2003/099985 A, to the entiredisclosure of which reference is hereby made.

In a preferred embodiment, the at least one first phase (1) of thedetergent or cleaning agent according to the invention, particularly ofthe dishwashing detergent, preferably of the dishwashing detergent fordishwashers, is present in the form of a molded body, particularly acompacted body, especially a tablet. Especially preferably, the at leastone first phase (1) is a powdered detergent or cleaning agent that ispresent in the form of a compacted tablet.

Regardless of whether directly or indirectly (for example, through thepresence of a film, covering, or pouch as described above), the at leastone first phase (1) and the at least one second phase (2) can bearranged in any combination in relation to one another. For instance, afirst phase (1) can be arranged on or next to a second phase (2), asshown schematically in FIG. 1. In this embodiment, the detergent orcleaning agent according to the invention comprises one first phase (1)and one second phase (2). It is also conceivable for a first phase (1)to be surrounded by second phases (2), or vice versa, as illustrated inFIGS. 2a and 2b . The embedding of one phase in another, as is shownschematically in FIGS. 3a and 3b , is also included by the invention.Another, especially preferred arrangement is shown schematically in FIG.4. The second phase (2) is present in the form of a core that isembedded in the first phase (1). A pool shape of the solid first phase(1)—that is, a shape with a depression into which the second phase isintroduced—is especially preferred. The depression can be round,oval-shaped, or angular. Two depressions that are separated from oneanother can also be present which are filled with the at least onesecond phase (2). In this embodiment, the detergent or cleaning agentcomprises two second phases (2), and the two second phases can havedifferent compositions.

In principle, any geometry is possible. The rectangular shape shown hereis provided only for the sake of example. A round or oval shape of thetwo phases, or any polygonal configuration, is also conceivable.

Another object of the present application is a method for cleaning hardsurfaces, particularly of dishes, in which the surface is worked in aninherently known manner using a cleaning agent according to theinvention. In particular, the surface is brought into contact with thedetergent or cleaning agent according to the invention. The cleaning isperformed particularly using a cleaning machine, preferably adishwasher.

Another object of the present invention is also the use of a cleaningagent for cleaning hard surfaces, particularly of dishes.

In a preferred embodiment, the present application has a dishwashingdetergent for dishwashers as its object. In terms of the presentapplication, dishwashing detergents for dishwashers are compositionsthat can be used to clean soiled dishes in a mechanical dishwashingprocess. The dishwashing detergents for dishwashers according to theinvention thus differ from rinse aids, which are always used incombination with dishwashing detergents for dishwashers and do not haveany cleaning effect of their own.

Insofar as it is stated in the present application that the detergent orcleaning agent according to the invention comprises something overall orin the at least one first phase (1) or in the at least one second phase(2), this shall also be regarded as disclosing the fact that detergentsor cleaning agents or the respective phase can consist thereof. In thefollowing exemplary embodiment, the detergent or cleaning agentaccording to the invention is described in a non-limiting manner.

Exemplary Embodiments

Cleaning agents according to the invention were prepared which compriseda first phase and a second phase. Different geometries were realized.Moreover, cleaning agents were prepared that comprised two first phasesand one second phase. The following specifications refer to wt % (weightpercent) of active substance with respect to the total weight of therespective phase.

The first phases had the following composition:

Wt % Citrate, Na salt 10-25 Phosphonate (e.g., HEDP)  0-10 MGDA, Na salt 0-40 Disilicate, Na salt  0-40 Soda 10-30 Percarbonate, Na salt 5.0-20.0 Bleach catalyst (preferably Mn-based) 0.0-0.8 Bleach activator(e.g., TAED) 1.0-4.0 Nonionic surfactant(s), e.g., fatty alcohol 1.5-15.0 ethoxylate, preferably 20-40 EO, optionally end-Polycarboxylate 0.5-15  Cationic copolymer 0.0-1.0 Disintegrant - (e.g.,crosslinked PVP) 0.0-3.0 Protease preparation (tq) 1.0-7   Amylasepreparation (tq) 0.2-6   Silver anti-tarnishing agent (benzotriazole)0.0-1.0 Perfume 0.0-0.5 Dye solution 0.0-1.5 Zn salt (e.g., acetate)0.01-0.5  Sodium sulfate 0.0-25  Water 0.0-3   pH adjuster (e.g., citricacid) 0.0-5   Processing aids  0-10

Moreover, first phases were prepared which had the followingcomposition:

Wt % Citrate, Na salt 15-20 Phosphonate (e.g., HEDP) 2.5-7.5 MGDA, Nasalt  0-25 Disilicate, Na salt  5-35 Soda 10-25 Percarbonate, Na salt10-15 Bleach catalyst (preferably Mn-based) 0.02-0.5  Bleach activator(e.g., TAED) 1-3 Nonionic surfactant(s), e.g., fatty alcohol 2.5-10 ethoxylate, preferably 20-40 EO, optionally Polycarboxylate  4-10Cationic copolymer   0-0.75 Disintegrant - (e.g., crosslinked PVP)  0-1.5 Protease preparation (tq) 1.5-5   Amylase preparation (tq)0.5-3   Silver anti-tarnishing agent (benzotriazole)   0-0.5 Perfume0.05-0.25 Dye solution 0.0-1   Zn salt (e.g., acetate) 0.1-0.3 Sodiumsulfate 0.0-10  Water 0.0-1.5 pH adjuster (e.g., citric acid)   0-1.5Processing aids 0-5

The first phases were present in the form of a compacted tablet with arecess on one side. A liquid composition was poured into these whichyielded the second phase after curing. The cleaning agent that wasobtained was in the form as shown in FIG. 4. There were additional firstphases without a recess. Here, a second phase was brought into directcontact with the surface of the first phase.

The second phases had the following composition:

wt % Glycerin 10-50 Propanediol (preferably 1,3-propanediol) 10-50Polycarboxylate homo- and/or copolymer with  0-30 sulfonicacid-containing groups Nonionic surfactant(s), e.g., fatty alcoholethoxylate,  0-40 preferably 20-40 EO, optionally end-cappedPolyethylene glycol avg. Mr 1,000-2,000  0-20 Thickener (preferablygelatin or PVA)  5-50 Processing aids  0-10 Dye solution 0.0-1.5

Additional second phases having the following composition were prepared:

Wt % Glycerin 20-45 Propanediol (preferably 1,3-propanediol) 10-30Polycarboxylate; homo- and/or copolymer with  5-20 sulfonicacid-containing groups Nonionic surfactant(s), e.g., fatty alcoholethoxylate,  5-25 preferably 20-40 EO, optionally end-cappedPolyethylene glycol avg. Mr 1,000-2,000 0-8 Thickener (preferablygelatin or PVA) 10-20 Processing aids 0-5 Dye solution 0.0-0.5

The first and second phases were able to be combined with each other inany way. The spatial configuration of the second phase, which was aliquid after the mixing of the ingredients and dimensionally stablewithin a setting time of about 10 to 15 minutes, was predetermined bythe spatial configuration of the first phase and by shapes that arecustomary in the trade or self-designed. The liquid second phase wasintroduced into these molds and, after the setting time, the molds wereremoved without altering the second phase. Unlimited geometries of thesecond phase were made possible in this way.

TABLE 1 Examples of compositions of a second phase A1 A2 1,2-propanediol0.0 31 1,3-propanediol 31 0.0 Trisodium citrate * 2 H₂O 8 8 Glycerin 3131 Gelatin 60 Bloom 15 15 Nonionic surfactant 15 15 Setting time (20°C.)/min 5 20 Feel of the surface after 12 h of storage at 20° C. DryMoist

It can be seen from table 1 that 1,3-propanediol leads to a quickersetting of the dimensionally stable second phase.

TABLE 2 Additional examples of compositions of a second phase B1 B2 B3B4 1,2-propanediol 45 0.0 0.0 0.0 1,3-propanediol 0.0 45 0.0 0.0 1,3butanediol 0.0 0.0 45 0.0 1,4 butanediol 0.0 0.0 0.0 45 Glycerin 29 2929 29 Maltodextrin 5 5 5 5 Gelatin 60 Bloom 20 20 20 20 Nonionicsurfactant 1 1 1 1 Setting time (20° C.)/min 15 5 5 5 TransparencyTransparent Transparent Opaque Opaque Feel of the surface Dry Dry GreasyGreasy after 12 h of storage at 20

TABLE 3 Storage stability after storage of the second phase for 12 daysat 40° C. (poured into the depression of a dishwashing detergent tablet)C₁ C₂ 1,2-propanediol 47 0.0 1,3-propanediol 0.0 47 Glycerin 20 20Sulfonic acid group-containing polymer 8 8 (ground) Gelatin 180 Bloom 2525 Setting time (20° C.)/min 15 5 After storage, 40° C., 12 days:Adhesion between first and second phase Low Very good Feel/visualappearance of the second Dry, shiny, Dry, shiny, phase (surface)transparent transparent

What is claimed is:
 1. A detergent or cleaning agent comprising at leastone first phase and at least one second phase that is different fromsaid first phase, wherein the at least one first phase is solid andparticularly compressed and the at least one second phase comprises atleast one polymer as well as at least one polyvalent alcohol, andwherein the at least one second phase is linear-elastic and transparent.2. The detergent or cleaning agent as set forth in claim 1, wherein theat least one second phase comprises at least two polyvalent alcohols,with a first polyvalent alcohol comprising an alkanetriol, and a secondpolyvalent alcohol comprising an alkanediol.
 3. The detergent orcleaning agent as set forth in claim 2, wherein the first polyvalentalcohol is a C₃ to C₈ alkanetriol.
 4. The detergent or cleaning agent asset forth in claim 2, wherein the second polyvalent alcohol is a C₃ toC₈ alkanediol.
 5. The detergent or cleaning agent as set forth in claim2, wherein the two OH groups of the alkanediol are not arranged onimmediately adjacent C atoms of the alkyl chain, and that three or fourcarbon atoms are located between the two OH groups.
 6. The detergent orcleaning agent as set forth in, claim 1 wherein the at least one secondphase is substantially water-free.
 7. The detergent or cleaning agent asset forth in claim 1, wherein the at least one second phase comprisesgelatin and/or PVA as a polymer.
 8. The detergent or cleaning agent asset forth in claim 1, wherein the at least one first phase and/or the atleast one second phase comprises at least one surfactant.
 9. Thedetergent or cleaning agent as set forth in claim 1, wherein thedetergent or cleaning agent is present in the form of a tablet, with theweight ratio of the at least one first phase to the at least one secondphase being 20:1 to 8:1.
 10. The detergent or cleaning agent as setforth in claim 2, wherein the at least one second phase comprises atleast two polyvalent alcohols, with a first polyvalent alcohol being aC₃ to C₁₀ alkanetriol, and a second polyvalent alcohol being a C₃ to C₁₀alkanediol.
 11. The detergent or cleaning agent as set forth in claim 3,wherein the first polyvalent alcohol is a C₃ to C₆ alkanetriol.
 12. Thedetergent or cleaning agent as set forth in claim 11, wherein the firstpolyvalent alcohol is glycerin.
 13. The detergent or cleaning agent asset forth in claim 11, wherein the first polyvalent alcohol is1,1,1-trimethylolpropane.
 14. The detergent or cleaning agent as setforth in claim 11, wherein the first polyvalent alcohol is2-amino-2-(hydroxymethyl)-1,3-propanediol.
 15. The detergent or cleaningagent as set forth in claim 4, wherein the second polyvalent alcohol isa C₃ to C₅ alkanediol.
 16. The detergent or cleaning agent as set forthin claim 8, wherein the at least one first phase and/or the at least onesecond phase comprises at least one nonionic surfactant.